The accumulation of sedimentary PCBs in The accumulation of sedimentary PCBs in bullfrog (bullfrog (RanaRana catesbeianacatesbeiana) tadpoles from ) tadpoles from

the Upper Hudson Riverthe Upper Hudson River

Joseph C. SteinbacherJoseph C. Steinbacher11, Christopher J. Balk, Christopher J. Balk22, , Kathryn A. JahnKathryn A. Jahn33, Thomas M. Brosnan, Thomas M. Brosnan11

11National Oceanic & Atmospheric AdministrationNational Oceanic & Atmospheric AdministrationSilver Spring, MarylandSilver Spring, Maryland

22New York State Department of Environmental ConservationNew York State Department of Environmental ConservationGloversville, New YorkGloversville, New York

33United States Fish & Wildlife ServiceUnited States Fish & Wildlife ServiceCortland, New YorkCortland, New York

Study ObjectivesStudy Objectives

•• Screening level Screening level survey of PCB survey of PCB contaminationcontamination

•• Preliminary Preliminary measure for measure for basing future basing future investigationsinvestigations

Bullfrog EcologyBullfrog Ecology•• Largest North American frogLargest North American frog•• Native to Central and Eastern United StatesNative to Central and Eastern United States•• Highly aquaticHighly aquatic•• CarnivorousCarnivorous•• Long lived (up to 10 yrs)Long lived (up to 10 yrs)•• Breed during late Spring in Breed during late Spring in

permanent water bodiespermanent water bodies•• Egg masses attached to Egg masses attached to

submerged vegetationsubmerged vegetation

Bullfrog Life StagesBullfrog Life Stages

Frog SpawnFrog Spawn

PrePre--limblimb

Limb BudLimb Bud

Hind LimbHind Limb

MetamorphMetamorph

**GosnerGosner KL (1960) A simplified table for staging anuran embryos KL (1960) A simplified table for staging anuran embryos and larvae with notes on identification. and larvae with notes on identification. Herpetologica Herpetologica 16: 18316: 183--190.190.

Bullfrog TadpolesBullfrog Tadpoles•• Hatch out in SummerHatch out in Summer•• Over winter in sedimentsOver winter in sediments•• May reach lengths greater than 8 cmMay reach lengths greater than 8 cm•• Primarily herbivorous Primarily herbivorous –– organic debris, organic debris,

algae, plant tissue, detritusalgae, plant tissue, detritus

Study SitesStudy Sites

Sampling SynopsisSampling Synopsis

•• Samples collected AugustSamples collected August--September 2003September 2003•• Sediment collected from 9 sites (2 reference)Sediment collected from 9 sites (2 reference)•• Composited Composited sediment samples (n = 9)sediment samples (n = 9)•• 155 tadpoles collected from 8 sites (6 study, 2 155 tadpoles collected from 8 sites (6 study, 2

reference)reference)•• Individuals wereIndividuals were compositedcomposited based on based on

developmental stage (42 developmental stage (42 compositedcomposited samples, n = samples, n = 1 1 -- 12)12)

•• Tadpole gut coils were removed prior to analysisTadpole gut coils were removed prior to analysis

Sampling

Total Total PCBsPCBs

Sediment [PCB]Sediment [PCB]

Site 7 Site 4 Site 3 Site 6 Site 5 Site 8 Site 1 Site 9

PCB

Con

cent

ratio

n (p

pm)

0.01

0.1

1

10

100

Reference SitesHudson River Study Sites

Site 7 Site 4 Site 3 Site 6 Site 5 Site 8 Site 1 Site 9

PCB

Con

cent

ratio

n (p

pm)

0.01

0.1

1

10

100

Reference SitesHudson River Study Sites

Upstream Downstream

Tadpole [PCB]Tadpole [PCB]

Site 7 Site 4 Site 3 Site 6 Site 5 Site 8 Site 1 Site 9

PCB

Con

cent

ratio

n (p

pm)

0.01

0.1

1

10

100

Reference SitesHudson River Study Sites

Site 7 Site 4 Site 3 Site 6 Site 5 Site 8 Site 1 Site 9

PCB

Con

cent

ratio

n (p

pm)

0.01

0.1

1

10

100

Reference SitesHudson River Study Sites

Upstream Downstream

Sediment & TadpolesSediment & Tadpoles

Sediment PCB Concentration (ppm)

0 10 20 30 40 50 60 70

Tadp

ole

PCB

Con

cent

ratio

n (p

pm)

0

1

2

3

4

5

6

y = 0.07x + 503R2 = 0.89

Sediment PCB Concentration (ppm)

0 10 20 30 40 50 60 70

Tadp

ole

PCB

Con

cent

ratio

n (p

pm)

0

1

2

3

4

5

6

y = 0.07x + 503R2 = 0.89

Tadpole Tadpole Developmental Developmental

Stage [PCB]Stage [PCB]

Pre-limb Limb Bud Hind Limb Metamorph

PCB

Con

cent

ratio

n (p

pm)

0.01

0.1

1

10

100

Pre-limb Limb Bud Hind Limb Metamorph

PCB

Con

cent

ratio

n (p

pm)

0.01

0.1

1

10

100

Hudson River Study Sites

Reference Sites

Pre-limb Limb Bud Hind Limb Metamorph

PCB

Con

cent

ratio

n (p

pm)

0.01

0.1

1

10

100

Pre-limb Limb Bud Hind Limb Metamorph

PCB

Con

cent

ratio

n (p

pm)

0.01

0.1

1

10

100

Hudson River Study Sites

Reference Sites

PCB CongenersPCB Congeners•• 48 PCB congeners selected for quantification48 PCB congeners selected for quantification•• Selected congeners are found, historically, in PCB Selected congeners are found, historically, in PCB

composition of various Hudson River physical and composition of various Hudson River physical and biological samplesbiological samples

•• 12 12 ‘‘DioxinDioxin--likelike’’ PCB congeners included among the 48PCB congeners included among the 48

PCB CongenersPCB Congeners

16716712612677771691698181

15815812312374741571571181187070

1891891561561141146666187187153153110110565618318315115110510552521801801491491011014949

201201177177146146999947471951951741741381389595454531/2831/28

20920920620619419417017012812887874444181888DecaDecaNonaNonaOctaOctaHeptaHeptaHexaHexaPentaPentaTetraTetraTri Tri Di Di

PCB PCB CongenersCongeners Upper Study

Sites

Lower StudySites

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.10

0.12

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.10

0.12

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.10

0.12

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.10

0.12

Hudson River Hudson River Study Site Study Site

Sediment PCB Sediment PCB Congener Congener

CompositionComposition

Upper Study Sites

Lower Study Sites

831/28

47,49,52

831/28

47,49,52

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.10

0.12

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.10

0.12

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.10

0.12

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.10

0.12

Reference Site Reference Site Sediment PCB Sediment PCB

Congener Congener CompositionComposition

Site 1

Site 9

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.10

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.10

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.10

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.10

Hudson River Hudson River Study Site Study Site

Tadpole PCB Tadpole PCB Congener Congener

CompositionComposition

Upper Study Sites

LowerStudy Sites

31/28

47,49,52

31/28

47,49,52

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.100.400.500.600.70

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.100.400.500.600.70

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.100.400.500.600.70

Frac

tion

of T

otal

0.00

0.02

0.04

0.06

0.08

0.100.400.500.600.70

Reference Site Reference Site Tadpole PCB Tadpole PCB

Congener Congener CompositionComposition

Site 1

Site 9

0.00

0.02

0.04

0.06

0.08

0.10

818

31/28

44

45

4749

52

56

667074

7781

87

9599

101

105

110

114

118

123126128

138

146149151153

156157158167169170174177180183187189194195201206209

Fraction of Total (Sediment)

0.00 0.02 0.04 0.06 0.08 0.10

Frac

tion

of T

otal

(Tad

pole

s)

0.00

0.02

0.04

0.06

0.08

0.10

818

31/28

44

45

4749

52

56

667074

7781

87

9599

101

105110

114

118

123126128

138

146149151153

156157158167169170174177180183187189194195201206209

0.00

0.02

0.04

0.06

0.08

0.10

818

31/28

44

45

4749

52

56

667074

7781

87

9599

101

105

110

114

118

123126128

138

146149151153

156157158167169170174177180183187189194195201206209

Fraction of Total (Sediment)

0.00 0.02 0.04 0.06 0.08 0.10

Frac

tion

of T

otal

(Tad

pole

s)

0.00

0.02

0.04

0.06

0.08

0.10

818

31/28

44

45

4749

52

56

667074

7781

87

9599

101

105110

114

118

123126128

138

146149151153

156157158167169170174177180183187189194195201206209

Sediment Sediment vs vs Tadpole PCB Tadpole PCB Composition Composition (One to One)(One to One)

UpperStudy Sites

LowerStudy Sites

Tadpole Tadpole :: Sediment Ratios Sediment Ratios ((TSRsTSRs))

Sediment OrganicSediment OrganicCarbon Carbon vs vs [PCB][PCB]

Tadpole LipidTadpole LipidContent Content vs vs [PCB][PCB]

Organic Carbon (%)0 2 4 6 8 10 12 14 16 18

Sedi

men

t PC

B C

once

ntra

tion

(ppm

)

0

10

20

30

40

50

60

70

Lipid Content (%)

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

Tadp

ole

PCB

Con

cent

ratio

n (p

pm)

0

2

4

6

8

10

y = -781.2x + 18870R2 = 0.02

y = -17.73x + 1519R2 = 0.01

Organic Carbon (%)0 2 4 6 8 10 12 14 16 18

Sedi

men

t PC

B C

once

ntra

tion

(ppm

)

0

10

20

30

40

50

60

70

Lipid Content (%)

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

Tadp

ole

PCB

Con

cent

ratio

n (p

pm)

0

2

4

6

8

10

y = -781.2x + 18870R2 = 0.02

y = -17.73x + 1519R2 = 0.01

Tadpole Tadpole : : SedimentSediment

Ratios (Ratios (TSRsTSRs))

Frac

tion

of T

otal

(Tad

pole

)

0.00

0.02

0.04

0.06

0.08

0.10

8 181/28 44 45 47 49 52 56 66 70 74 77 81 87 95 99 101

105

110

114

118

123

126

128

138

146

149

151

153

156

157

158

167

169

170

174

177

180

183

187

189

194

195

201

206

209

Frac

tion

of T

otal

(Sed

imen

t)

0.00

0.02

0.04

0.06

0.08

0.10

Frac

tion

of T

otal

(Tad

pole

)

0.00

0.02

0.04

0.06

0.08

0.10

8 181/28 44 45 47 49 52 56 66 70 74 77 81 87 95 99 101

105

110

114

118

123

126

128

138

146

149

151

153

156

157

158

167

169

170

174

177

180

183

187

189

194

195

201

206

209

Frac

tion

of T

otal

(Sed

imen

t)

0.00

0.02

0.04

0.06

0.08

0.10

Tadpole PCBs Tadpole PCBs (normalized to total(normalized to total))

Sediment PCBs Sediment PCBs (normalized to total)(normalized to total)

TSR

0

2

4

6

8

10

12

14

16

18

TSR

0

2

4

6

8

10

12

14

16

18

TSR

0

2

4

6

8

10

12

14

16

18

TSR

0

2

4

6

8

10

12

14

16

18

TSRsTSRs

Hudson RiverStudy Sites

Site 1

Log

TSR

-1.0

-0.5

0.0

0.5

1.0

1.5

8

18

31/28

44

45

474952

5666 70

74

879599101

105

110114

118

128 138146149151

153

156

157158

167170174177

180183187

189

194195

201

206 209

Log Kow5 6 7 8 9 10

Log

TSR

-1.0

-0.5

0.0

0.5

1.0

1.5

31/28

44

47

495256

6670

748795

99101105

110

118128

138146 149

151

153

156158167

170174177

180

183

187

Log

TSR

-1.0

-0.5

0.0

0.5

1.0

1.5

8

18

31/28

44

45

474952

5666 70

74

879599101

105

110114

118

128 138146149151

153

156

157158

167170174177

180183187

189

194195

201

206 209

Log Kow5 6 7 8 9 10

Log

TSR

-1.0

-0.5

0.0

0.5

1.0

1.5

31/28

44

47

495256

6670

748795

99101105

110

118128

138146 149

151

153

156158167

170174177

180

183

187

Log Log Kow vs Kow vs Log TSRLog TSR

Hudson RiverStudy Sites

Site 1

Study Site Log Study Site Log Kow vs Kow vs Log TSRLog TSR

Log Kow

5.0 5.5 6.0 6.5 7.0 7.5 8.0

Log

TSR

-1.0

-0.5

0.0

0.5

1.0

1.5

Log Kow

5.0 5.5 6.0 6.5 7.0 7.5 8.0

Log

TSR

-1.0

-0.5

0.0

0.5

1.0

1.5DiDi

TriTri

TetraTetra

PentaPenta

HexaHexa

HeptaHepta

OctaOcta

ConclusionsConclusions•• Hudson River bullfrog tadpoles are contaminated with PCBsHudson River bullfrog tadpoles are contaminated with PCBs•• Tadpole PCB body burdens and congener distributions reflect Tadpole PCB body burdens and congener distributions reflect

sediment PCB loads and compositionsediment PCB loads and composition•• Sediment and tadpole PCB congener distributions varied little Sediment and tadpole PCB congener distributions varied little

within and between study siteswithin and between study sites•• Reference site sediment Reference site sediment

and tadpole PCB congener and tadpole PCB congener composition differed composition differed markedly from study sitesmarkedly from study sites

•• The majority of sediment The majority of sediment PCB congeners are found PCB congeners are found in greater relative in greater relative fractions in collocated fractions in collocated tadpole tissuestadpole tissues